JPH08245619A - Using method for 2,2,6,6-tetramethylpiperidine derivative as stabilizer of organic material against light, heat, and oxidation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new 2,2,6,6-tetramethylpiperidine derivative capable of imparting excellent stability to light, heat and oxidation to organic materials and useful as a stabilizing agent for the organic materials, especially synthetic polymers.

SOLUTION: This compound is represented by formula I [X is a group represented by formula II (R₆ is H, a 1-18C alkyl, a 5-12C cycloalkyl or the like; R₇ is H, a 1-8C alkyl, OH or the like) or the like; R₁ and R₅ are each H, a 1-18C alkyl, a 5-12C cycloalkyl or the like; R₂, R₃ and R₄ are each a 2-12C alkylene; (n) is 0 or 1] e.g. NI,NII,NIII-tris{2-[N-(2,2,6,6-tetramethylpiperidin-4-yl)- butylamino]-4-[bis(2,2,6,6-tetramethylpiperidin-4-yl)amino]-triazin-6-lyl}- diethylenetriamine. The compound represented by formula I is obtained by reacting cyanuric chloride with a compound represented by the formula R₁-NH- R₂-NH-(R₃-NH)_n-R₄-NH-R₅ with a compound represented by formula III and a compound represented by formula IV.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to novel piperidinetriazine compounds and organic materials against light, heat or oxidation, in particular their use as stabilizers of synthetic polymers, and organic materials stabilized by this method. .

[0002]

BACKGROUND OF THE INVENTION Stabilization of synthetic polymers with triazine compounds containing 2,2,6,6-tetramethylpiperidine groups has been described in a number of patented invention specifications, particularly US Pat. 57-38589
And U.S. Pat. Nos. 4,816,507 and 4,997,938.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention relates to novel compounds represented by the following formula (I).

Embedded image [In the formula, n represents 0 or 1, and X represents the following formula (I
I)

[Chemical 6] And R ₁ and R ₅ may be the same or different and may be a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, unsubstituted or 1, 2 or 3 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, unsubstituted or substituted on the phenyl group by an alkyl group having 1, 2 or 3 carbon atoms having 1 to 4 carbon atoms Represents a phenylalkyl group of the formulas 7 to 9, or R ₁ and R ₅ are represented by the following formula (III)

[Chemical 7] And R ₂ , R ₃ and R ₄ may be the same or different and each represents an alkylene group having 2 to 12 carbon atoms, R ₆ is a hydrogen atom or alkyl having 1 to 18 carbon atoms. Groups, unsubstituted or substituted with 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, alkenyl groups having 3 to 6 carbon atoms, unsubstituted or phenyl Represents a phenylalkyl group having 7 to 9 carbon atoms, which is substituted by an alkyl group having 1 to 2 or 3 carbon atoms and having 1 to 4 carbon atoms, and R ₇ is a hydrogen atom or 1 carbon atom
To 8 _{alkyl, O ·, OH, CH 2} CN, alkoxy groups of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, an alkenyl group of 6 C 3 -C, unsubstituted or phenyl Represents a phenylalkyl group having 7 to 9 carbon atoms which is substituted by an alkyl group having 1 to 2 or 3 carbon atoms and having 1 to 4 carbon atoms, or R ₇ is an aliphatic group having 1 to 8 carbon atoms When an acyl group is represented, n is 1 and R ₁ and R ₅ are groups of formula (III), X is of the formula (IV)

Embedded image (Wherein R ₆ and R ₇ have the previously defined meanings). ]

Examples of alkyl radicals containing up to 18 carbon atoms are the following: methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, pentyl. Group, 2-pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, tertiary-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
A hexadecyl group and an octadecyl group.

Examples of the cycloalkyl group having 5 to 12 carbon atoms which is unsubstituted or substituted by an alkyl group having 1 to 2 or 3 carbon atoms and having 1 to 4 carbon atoms include the following cyclopentyl group, methylcyclopentyl group and dimethyl group. A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a tert-butylcyclohexyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group. It is preferably an unsubstituted or substituted cyclohexyl group.

1, on an unsubstituted or phenyl group,
Examples of phenylalkyl groups having 7 to 9 carbon atoms which are substituted by 2 or 3 alkyl groups having 1 to 4 carbon atoms include the following benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, A 3-butylbenzyl group and a 2-phenylethyl group. A benzyl group is preferred.

Examples of alkylene groups containing up to 12 carbon atoms are the following: ethylene, propylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, tetramethylene, pentamethylene. Methylene group, hexamethylene group, trimethylhexamethylene group,
An octamethylene group, a decamethylene group, and a dodecamethylene group.

Examples of alkenyl groups having 3 to 6 carbon atoms are allyl group, 2-methylallyl group, butenyl group and hexenyl group. Preferred is an alkenyl group in which the 1-position carbon atom is saturated, and particularly preferred is an allyl group.

Examples of alkoxy groups containing up to 18 carbon atoms are: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,
A heptoxy group, an octoxy group, a decyloxy group, a dodecyloxy group, a tetradecyloxy group, a hexadecyloxy group and an octadecyloxy group. Preferred examples are alkoxy groups having 6 to 12 carbon atoms, especially heptoxy and octoxy groups.

Examples of the cycloalkoxy group having 5 to 12 carbon atoms are cyclopentoxy group, cyclohexoxy group, cycloheptoxy group, cyclooctoxy group, cyclododeroxy group and cyclododecyloxy group. Preferred are a cyclopentoxy group and a cyclohexoxy group.

Examples of aliphatic acyl groups containing up to 8 carbon atoms are the following: acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, acryloyl and crotonyl. . Preferred are alkanoyl groups having 1 to 8 carbon atoms and alkenoyl groups having 3 to 8 carbon atoms.

The preferred definition of R ₇ is hydrogen atom, alkyl group having 1 to 4 carbon atoms, OH, alkoxy group having 6 to 12 carbon atoms, cycloalkoxy group having 5 to 8 carbon atoms, allyl group and benzyl group. Alternatively, it is an acetyl group, especially a hydrogen atom or a methyl group.

X is preferably a group of formula (II).

Preferred compounds of formula (I) are those in which X represents a group of formula (II), R ₁ and R ₅ may be the same or different and are hydrogen atom, 1 to 12 carbon atoms.
Represents an alkyl group of 5 to 7 carbon atoms, a cycloalkyl group of 5 to 7 carbon atoms or a phenylalkyl group of 7 to 9 carbon atoms, R ₂ , R ₃ and R ₄ may be the same or different and have 2 to 6 carbon atoms. R ₆ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, or 7 to 9 carbon atoms. Is a compound representing a phenylalkyl group.

Particularly preferred compounds of formula (I) are those wherein:
X represents a group of formula (II), R ₁ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group or a benzyl group, and R ₂ , R ₃ And R _{4, which} may be the same or different, each represents an alkylene group having 2 to 6 carbon atoms, and R ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, an allyl group or a benzyl group. It is a compound.

[0016]

Compounds of formula (I) of particular interest are those wherein X represents a group of formula (II), R ₁ and R ₅
May be the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₂ , R ₃ and R ₄ may be the same or different and represent an alkylene group having 2 to 3 carbon atoms. , R ₆ has 1 carbon atom
To represent 4 alkyl, and R ₇ is a compound represents a hydrogen atom or a methyl group.

The preferred compounds of formula (I) also have the formula:
n is 1; R ₁ and R ₅ are groups of formula (III) and X is a group of formula (IV).

More preferred compounds of formula (I) are those in which n represents ₁ , R ₁ and R ₅ represent a group of formula (III), X represents a group of formula (IV) and R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkylene group having 2 to 6 carbon atoms, and R ₆ is a hydrogen atom,
A compound representing an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

Compounds of formula (I) of particular interest are also
In the formula, n represents 1, R ₁ and R ₅ represent a group of formula (III), X represents a group of formula (IV), and R ₂ , R ₃ and R ₄ may be the same or different. , 2 carbon atoms
To represent a 6 alkylene group, and R ₆ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a compound representative of the allyl or benzyl group.

More particularly preferred compounds of formula (I) are
In the formula, n represents 1 and R₁And R_Five Is of formula (III)
Represents a group, X represents a group of formula (IV), R₂, R₃ And
And R _Four May be the same or different and have 2 carbon atoms
Represents an alkylene group of 1 to 3 and R₆ Has 1 carbon atom
Represents an alkyl group of Ishi 4, and R₇ Is a hydrogen atom
Is a compound that represents a methyl group.

Examples of compounds of formula (I) are N ^I , N ^II , N
^III -tris [2- (N- (2,2,6,6-tetramethylpiperidin-4-yl) -butylamino) -4-
(Bis [2,2,6,6-tetramethylpiperidin-4
- yl] amino) - triazinyl-6-yl] - ^{diethylenetriamine, N I, N II, N} III - tris [2-(N
-(1,2,2,6,6-pentamethylpiperidini-4
-Yl) -butylamino) -4- (bis [1,2,2,2
6,6-Pentamethylpiperidin-4-yl] amino)
-Triazin-6-yl] -diethylenetriamine, N
^I , N ^II , N ^III -Tris [2- (N- (2,2,6,
6-Tetramethylpiperidin-4-yl) -butylamino) -4- (bis [2,2,6,6-tetramethylpiperidin-4-yl] amino) -triazin-6-yl]
- di-hexamethylene ^{triamine, N I, N II, N} III -
Tris [2- (N- (1,2,2,6,6-pentamethylpiperidin-4-yl) -butylamino) -4- (bis [1,2,2,6,6-pentamethylpipet Rigini-4
- yl] amino) - triazinyl-6-yl] - di-hexamethylene ^{triamine, N I, N II, N} III - tris [2
-(N- (2,2,6,6-tetramethylpiperidini-
4-yl) -ethylamino) -4- (bis [2,2,2
6,6-Tetramethylpiperidin-4-yl] amino)
-Triazin-6-yl] -diethylenetriamine, N
^I , N ^II , N ^III -Tris [2- (N- (1,2,2,
6,6-Pentamethylpiperidin-4-yl) -ethylamino) -4- (bis [1,2,2,6,6-pentamethylpiperidin-4-yl] amino) -triazin-6
- yl] - ^{diethylenetriamine, N I, N II, N} III
-Tris [2- (N- (2,2,6,6-tetramethylpiperidin-4-yl) -ethylamino) -4- (bis [2,2,6,6-tetramethyl-piperidin-4] - yl] amino) - triazinyl-6-yl] - di-hexamethylene ^{triamine, N I, N II, N} III - tris [2-
(N- (1,2,2,6,6-pentamethylpiperidin-4-yl) -ethylamino) -4- (bis [1,2,
2,6,6-pentamethyl - piperidin-4-yl] amino) - triazinyl-6-yl] - di-hexamethylene ^{triamine, N I, N II, N} III - tris [2-(N-
(2,2,6,6-Tetramethylpiperidin-4-yl) -dodecylamino) -4- (bis [2,2,6,6
- tetramethyl - piperidin-4-yl] amino) - triazinyl-6-yl] - diethylenetriamine, N ^I,
N ^II , N ^III -Tris [2- (N- (1, 2, 2, 6,
6-Pentamethylpiperidin-4-yl) -dodecylamino) -4- (bis [1,2,2,6,6-pentamethyl-piperidin-4-yl] amino) -triazin-6
- yl] - ^{diethylenetriamine, N I, N II, N} III
-Tris [2- (N- (2,2,6,6-tetramethylpiperidin-4-yl) -dodecylamino) -4- (bis [2,2,6,6-tetramethyl-piperidin-4 −
Yl] amino) - triazinyl-6-yl] - di-hexamethylene ^{triamine, N I, N II, N} III - tris [2-
(N- (1,2,2,6,6-pentamethylpiperidin-4-yl) -dodecylamino) -4- (bis [1,
2,2,6,6-pentamethyl - piperidin-4-yl] amino) - triazinyl-6-yl] - di-hexamethylene ^{triamine, N I, N II, N} III, N IV - tetrakis [2-(N- (2,2,6,6-Tetramethylpiperidin-4-yl) -butylamino) -4- (bis [2,2
2,6,6-Tetramethyl-piperidin-4-yl] amino) -triazin-6-yl] -1,5,8,12-
Tetraazacyclododecane ^{dodecane, N I, N II, N} III, N IV - tetrakis [2- (N- (1,2,2,6,6- pentamethyl piperidine Gini-4-yl) - butylamino) -4- (Bis [1,2,2,6,6-pentamethyl-piperidin-
4-yl] amino) -triazin-6-yl] -1,
5,8,12-Tetraazadodecane, N ^I , N ^II , N
^III , N ^IV -Tetrakis [2- (N- (2,2,6,6
-Tetramethylpiperidin-4-yl) -ethylamino) -4- (bis [2,2,6,6-tetramethyl-piperidin-4-yl] amino) -triazin-6-yl] -1,5 , 8,12-Tetraazadodecane, N ^I ,
N ^II , N ^III , N ^IV -tetrakis [2- (N- (1,
2,2,6,6-pentamethylpiperidin-4-yl)
-Ethylamino) -4- (bis [1,2,2,6,6-
Pentamethyl - piperidin-4-yl] amino) - triazinyl-6-yl] -1,5,8,12- tetraazacyclododecane ^{dodecane, N I, N II, N} III, N IV - tetrakis [2-
(N- (2,2,6,6-tetramethylpiperidin-4
-Yl) -dodecylamino) -4- (bis [2,2,2
6,6-tetramethyl - piperidin-4-yl] amino) - triazinyl-6-yl] -1,5,8,12- tetraazacyclododecane ^{dodecane, N I, N II, N} III, N IV - tetrakis [2 -(N- (1,2,2,6,6-pentamethylpiperidin-4-yl) -dodecylamino) -4- (bis [1,2,2,6,6-pentamethyl-piperidinii-
4-yl] amino) -triazin-6-yl] -1,
5,8,12- tetraazacyclododecane dodecane, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] ^{-N I, N II, N III} , N IV - tetrakis - [2
4- (bis [N- (2,2,6,6-tetramethyl-piperidin-4-yl) -butylamino] -triazini-
6-yl] -1,5,8,12-tetraazadodecane,
N ^I, N ^IV - bis [1,2,2,6,6 pentamethyl piperidine Gini-4-yl] ^{-N I, N II, N III} , N IV -
Tetrakis- [2,4- (bis [N- (1,2,2
6,6-Pentamethyl-piperidin-4-yl) -butylamino] -triazin-6-yl] -1,5,8,1
2-tetraazacyclododecane dodecane, N ^I, N ^IV - bis [2,2,
6,6-tetramethyl-piperidine-dinitrate-4-yl] -N ^I,
N ^II , N ^III , N ^IV -tetrakis- [2,4- (bis [N- (2,2,6,6-tetramethyl-piperidin-
4-yl) -ethylamino] -triazin-6-yl]
-1,5,8,12- tetraazacyclododecane dodecane, N ^I, N ^IV
- bis [1,2,2,6,6 pentamethyl piperidine Gini-4-yl] ^{-N I, N II, N III} , N IV - tetrakis- - [2,4 (bis [N-(1, 2,2,6,6-Pentamethyl-piperidin-4-yl) -ethylamino]-
Triazinyl-6-yl] -1,5,8,12- tetraazacyclododecane dodecane, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] -N ^I, N ^II , N
^III , N ^IV -Tetrakis- [2,4- (bis [N-
(2,2,6,6-Tetramethyl-piperidin-4-yl) -dodecylamino] -triazin-6-yl]-
1,5,8,12-tetraazacyclododecane-dodecane, N ^I, N ^IV -
Bis [1,2,2,6,6-pentamethylpiperidiny-
4-yl] ^{-N I, N II, N III} , N IV - tetrakis -
[2,4- (bis [N- (1,2,2,6,6-pentamethyl-piperidin-4-yl) -dodecylamino]-
Triazinyl-6-yl] -1,5,8,12- tetraazacyclododecane dodecane, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] -N ^I, N ^II , N
^III , N ^IV -Tetrakis- [2,4- (bis [N-
(1,2,2,6,6-pentamethyl-piperidin-4
-Yl) -butylamino] -triazin-6-yl]-
1,5,8,12-tetraazacyclododecane-dodecane, N ^I, N ^IV -
Bis [2,2,6,6-tetramethylpiperidin-4-
Yl] ^{-N I, N II, N III} , N IV - tetrakis -
[2,4- (Bis [N- (1,2,2,6,6-pentamethyl-piperidin-4-yl) -ethylamino] -triazin-6-yl] -1,5,8,12-tetra Azadodekan, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] ^{-N I, N II, N III} ,
N ^IV -tetrakis- [2,4- (bis [N- (1,2,
2,6,6-Pentamethyl-piperidin-4-yl)-
Dodecylamino] -triazin-6-yl] -1,5
It is 8,12-tetraazadodecane.

Compounds of formula (I) of particular interest are N
^I , N ^II , N ^III -Tris [2- (N- (2,2,6,
6-tetramethylpiperidin-4-yl) -butylamino) -4- (bis [2,2,6,6-tetramethyl-piperidin-4-yl] amino) -triazin-6-yl] -diethylenetriamine, ^{N I, N II, N III} - tris [2-(N-(1,2,2,6,6 pentamethyl piperidine Gini-4-yl) - butylamino) -4- (bis [1,2, 2,6,6-pentamethyl-piperidin-4
- yl] amino) - triazinyl-6-yl] - ^{diethylenetriamine, N I, N II, N} III, N IV - tetrakis [2- (N- (2,2,6,6- tetramethyl-piperidine-dinitrate-4- Yl) -butylamino) -4- (bis [2,2
2,6,6-Tetramethyl-piperidin-4-yl] amino) -triazin-6-yl] -1,5,8,12-
Tetraazacyclododecane ^{dodecane, N I, N II, N} III, N IV - tetrakis [2- (N- (1,2,2,6,6- pentamethyl piperidine Gini-4-yl) - butylamino) -4- (Bis [1,2,2,6,6-pentamethyl-piperidin-
4-yl] amino) -triazin-6-yl] -1,
5,8,12- tetraazacyclododecane dodecane, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] ^{-N I, N II, N III} , N IV - tetrakis [ 2,4
-Bis [N- (2,2,6,6-tetramethyl-piperidin-4-yl] -butylamino) -triazin-6-
Il] -1,5,8,12-tetraazadodecane, N
^I , N ^IV -bis [1,2,2,6,6-pentamethylpiperidin-4-yl] -N ^I , N ^II , N ^III , N ^IV -tetrakis [2,4-bis [N- ( 1, 2, 2, 6, 6-
Pentamethyl-piperidin-4-yl] -butylamino) -triazin-6-yl] -1,5,8,12-tetraazadodecane.

The compounds of the present invention are, for example, cyanuric chloride and the following formulas (Va) to (Vc) in order and in an appropriate molar ratio.

[Chemical 9] (Wherein, R ₇ is. Representing a H) comprises the reaction of a compound represented by, known methods (e.g., U.S. Pat invention specification No. 4,108,829 and JP-A-57-38589 and U.S. Patent It can be manufactured according to the invention specifications 4816507 and 4997938).

The reaction is preferably carried out in an inert organic solvent such as toluene, xylene, trimethylbenzene, tertiary amyl alcohol, 1,2-dichloroethane or mixtures of tertiary amyl alcohol in any proportion with said solvent. Or in the presence of an inorganic base such as sodium or potassium hydroxide or sodium or potassium carbonate at a temperature between -20 ° C and 200 ° C, preferably between -10 ° C and 180 ° C.

Compounds of formula (I) in which R ₇ represents H may be prepared by this method. Then, by a method known from this compound, a corresponding compound in which R ₇ does not represent H can be obtained subsequently. Compounds of formula (Va) and (Vb) may be prepared by known methods. Formula (V
The compounds of c) are commercially available or can be prepared by known techniques.

As mentioned above, the compounds of the present invention are very effective in improving the resistance of organic materials, especially synthetic polymers and copolymers, to light, heat and oxidation.

Examples of organic materials that can be stabilized are: Polymers of mono- and di-olefins such as polypropylene, polyisobutylene, polybutene-1
-Enes, poly-4-methylpent-1-enes, polyisoprenes or polybutadienes, and polymers of cycloolefins such as cyclopentene or norbornene, polyethylene (which can optionally be crosslinked) such as high density polyethylene (HDPE), high density and high molecular weight. Polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (L
DPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, ie polymers of monoolefins such as those exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various methods, especially the following methods: a) (usually at elevated pressure and elevated temperature) ) Radical polymerization b) One or more than one IVb, V of the regular periodic table
Catalytic polymerization using a catalyst containing a Group b, VIb or VIII metal. These metals are usually oxides, halides, alcoholates, esters, ethers, amines, alkyls capable of one or more than one ligand, typically π- or σ-coordinated. , Alkenyl and /
Or having an aryl. These metal complexes may be in free form or immobilized on a support, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst can be used by itself in the polymerization, or another activator, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide or metal alkyloxane, can be used. Is an element of group Ia, IIa and / or IIIa of the periodic table. The activators may conveniently be modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually Phillips (Phi
llips), Standard Oil Indiana (Standard Oi
l Indiana), Ziegler- (Natta)
], TNZ (Dupont), metallocene or single site catalyst (SSC).

2. 1. A mixture of polymers described in
For example, a mixture of polypropylene and polyisobutylene,
A mixture of polypropylene and polyethylene (eg PP
/ HDPE, PP / LDPE) and mixtures of various types of polyethylene (eg LDPE / HDPE).

3. Copolymers of mono- and di-olefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and its low density polyethylene (LD
PE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / Octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and salts thereof ( Ionomers) and ethylene, propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene Mixture and 1 as well as the copolymers with one another; terpolymers of things like. Mixtures with the polymers mentioned in 1, for example polypropylene / ethylene-propylene-copolymers, LDPE / ethylene-vinyl acetate (EVA) copolymers, LDPE / ethylene acrylic acid (EAA) copolymers, LLDPE / EV.
A, LLDPE / EAA and random or alternating polyalkylene / carbon monoxide-copolymers; and other polymers and mixtures thereof such as polyamides.

4. Hydrocarbon resins (for example 5 to 9 carbon atoms) containing hydrogenated modifications thereof (eg tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).

6. Styrene or a copolymer of α-methylstyrene and a diene or an acrylic derivative, such as styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, Styrene / acrylonitrile / methyl acrylate; high impact strength mixtures of styrene copolymers with other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / Isoprene / styrene, styrene / ethylene / butylene / styrene, or styrene / ethylene / propylene / styrene

7. Graft copolymers of styrene or α-methylstyrene, such as polybutadiene on styrene, polybutadiene-styrene or polybutadiene-
Acrylonitrile to styrene like; polybutadiene to styrene and acrylonitrile (or methacrylonitrile); polybutadiene to styrene, acrylonitrile and methylmethacrylate; polybutadiene to styrene and maleic anhydride; polybutadiene to styrene, acrylonitrile and maleic anhydride or maleimide; polybutadiene Styrene and maleimide; polybutadiene with styrene and alkyl acrylates or methacrylates, ethylene / propylene / diene terpolymers with styrene and acrylonitrile, polyacrylates or polymethacrylates with styrene and acrylonitrile, acrylate / butadiene copolymers with styrene and acrylonitrile, and these 6. Mixtures with the copolymers listed under, for example the copolymer mixtures known as ABS, MBS, ASA and AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or chlorosulfonated polyethylenes, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers from halogen-containing vinyl compounds, such as polyvinyl chloride. , Polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids, and their derivatives, such as polyacrylates and polymethacrylates; impact modified polymethylmethacrylate, polyacrylamide and polyacrylonitrile with butyl acrylate.

10. Copolymers of the monomers listed in 9 above with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / halogenated vinyl copolymers, or acrylonitrile / alkyl methacrylate / butadiene. Terpolymer.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or their acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;
And those and 1. Copolymers with the olefins described under.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or their copolymers with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides.

15. Polyurethanes derived from hydroxy-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Diamine and dicarboxylic acid and / or
Or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams. For example, polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6 and polyamide 12/12, polyamide 11, polyamide 12, m-xylene diamine, and adipine. Aromatic polyamides obtained by condensation of acids; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally elastomers as modifiers, eg poly-
2,4,4- (trimethylhexamethylene) terephthalamide or poly-m-phenyleneisophthalamide;
Furthermore, copolymers of said polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or copolymers of these with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and EPDM or ABS Modified polyamides or copolyamides; polyamides condensed during processing (RIM-polyamide system).

17. Polyurea, Polyimide, Polyamide-
Imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-
Block-copolyether-esters derived from 1,4-dimethylol-cyclohexaneterephthalate, and polyhydroxybenzoates and polyethers containing hydroxy end groups; and also polyesters modified with polycarbonate or MBS.

19. Polycarbonates and polyester-carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas or melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Dry or non-dry alkyd resin.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and their halogen-containing modifications with low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylates, urethane acrylates or polyester-acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol A and bisphenol F
Of the diglycidyl ethers of the invention, which are cross-linked with conventional curing agents such as anhydrides or amines with or without accelerators.

27. Natural polymers such as cellulose,
Gum, gelatin and their chemically modified homologous derivatives such as cellulose acetate, cellulose propionate and butyrate, and cellulose ethers such as methyl cellulose; and rosins and their derivatives.

28. Mixtures (polyblends) of the aforementioned polymers, eg PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC
/ MBS, PC / ABS, PBTP / ABS, PC / A
SA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PU
R, POM / acrylate, POM / MBS, PPO /
HIPS, PPO / PA 6.6 and copolymers, PA
/ HDPE, PA / PP, PA / PPO, PBT / PC
/ ABS or PBT / PET / PC.

29. Natural and synthetic organic materials consisting of pure monomeric compounds or mixtures thereof, such as mineral oils,
Oils, fats and waxes based on animal or vegetable fats, oils and waxes or synthetic esters (eg phthalates, adipates, phosphates or trimellitates), and in any weight ratios used as plasticizers for polymers or as spinning formulation oils. Mixtures of synthetic esters with mineral oils, as well as aqueous emulsions of these materials.

30. Aqueous emulsions of natural or synthetic rubbers, such as natural latex, or latex of carboxylated styrene / butadiene copolymer.

The compounds of formula (I) are particularly suitable for improving the light, heat and oxidative stability of polyolefins, especially polyethylene or polypropylene.

The compounds of formula (I) can be used in mixtures with organic materials in various proportions, depending on the nature of the material to be stabilized, the end use and also on the presence of other stabilizers. .

Generally, for example, 0.01 to 5% by weight, based on the weight of the organic material to be stabilized, preferably 0.
It is expedient to use from 05 to 1% by weight of the compound of formula (I).

In general, the compound of formula (I) can be added to the polymeric material before, during or after the polymerization or crosslinking of said material.

The compounds of formula (I) can be incorporated into the polymeric materials in pure form or in the form of waxes, oils or polymer inclusions.

The compounds of formula (I) can be incorporated into the polymeric material by various methods, for example by dry mixing in the form of powders or by wet mixing in the form of solutions or suspensions or also in the form of masterbatches. The polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latex.

The materials stabilized with the compounds of formula (I) can be used, for example, for the production of moldings, films, tapes, monofilaments, fibers, lacquers and the like.

Other conventional additives for synthetic polymers, such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers corrosion inhibitors and metal deactivators are added to the compounds of the formula (I). Can be added, if appropriate, to the mixture of

Specific examples of additives that can be used for mixing with the compounds of formula (I) are as follows:

1. Antioxidants 1.1 Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-butyl-
4,6-Dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4
-N-butylphenol, 2,6-di-tert-butyl-4
-Isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4 , 6-Tricyclohexylphenol, 2,6-di-tert-butyl-4
-Methoxymethylphenol, nonylphenol with linear or branched side chains, for example 2,6-dinonyl-
4-methylphenol, 2,4-dimethyl-6- (1 '
-Methyl-undec-1'-yl) -phenol, 2,
4-Dimethyl-6- (1'-methyl-heptadecyl-1 '
-Yl) -phenol, 2,4-dimethyl-6- (1 '
-Methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenol,
For example, 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-
Methylphenol, 2,4-di-octylthiomethyl-
6-ethylphenol and 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinone and alkylated hydrate
Roquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6
-Diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tertiary Butyl-4-hydroxyphenyl stearate,
Bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocophenols such as α-tocophenol, β-tocophenol, γ-tocophenol, δ-tocophenol and mixtures thereof (vitamin E).

1.5 hydroxylated thiodiphenyl ether
Ether, e.g., 2,2'-thiobis (6-tert-butyl -
4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-) 2-methylphenol), 4,4 '
-Thio-bis (3,6-di-secondary-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) -disulfide.

1.6 Alkylidene bisphenols such as 2,2′-methylene-bis (6-tert-butyl-4-
Methylphenol), 2,2'-methylene-bis (6-
Tert-butyl-4-ethylphenol), 2,2'-methylene-bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylene-bis (4-
Methyl-6-cyclohexylphenol), 2,2'-
Methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4.
6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (α-methylbenzyl) -4- Nonylphenol], 2,2'-methylene-bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2,6
-Di-tert-butylphenol), 4,4'-methylene-
Bis (6-tert-butyl-2-methylphenol), 1,
1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-
5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-)
Hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3 ′ -Tert-butyl-
4'-hydroxyphenyl) butyrate], bis (3-
Tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-
2'-Hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1
-Bis (3,5-dimethyl-2-hydroxyphenyl)
Butane, 2,2-bis (3,5-di-tert-butyl-4-
Hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4
-N-dodecyl mercaptobutane, and 1,1,5
5-tetra- (5-tert-butyl-4-hydroxy-2-
Methylphenyl) pentane.

1.7. O-, N- and S-benzyl
Compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tridecyl-4-hydroxy. -3,5-Di-tert-butylbenzyl mercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) -dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) -sulfide and isooctyl-3,
5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylated maroney
DOO, for example dioctadecyl-2,2-bis (3,5-di - tert-butyl-2-hydroxybenzyl) - malonate, di - octadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl Benzyl) -malonate, di-dodecyl mercaptoethyl-2,2-bis (3,5-di-
Tert-butyl-4-hydroxybenzyl) -malonate,
And bis- [4- (1,1,3,3-tetramethylbutyl) -phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate.

1.9. Hydroxybenzyl aromatic compound
Object, for example 1,3,5-tris (3,5-di - tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di - tert Butyl-
4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-
Tertiary butyl-4-hydroxybenzyl) -phenol.

1.10. Triazine compounds, for example
2,4-bis-octyl mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5
-Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octyl mercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6
-Tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -Isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3,5)
-Di-tert-butyl-4-hydroxyphenylethyl)-
1,3,5-triazine, 1,3,5-tris (3,5
-Di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,
3,5-Tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate.

1.11. Base down phosphonates, for example dimethyl-2,5-di - tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di - tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di -Tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-
Ca salt of 4-hydroxy-3-methylbenzylphosphonate and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.12. Acylaminophenols , such as 4-hydroxyanilide lauric acid, 4-hydroxyanilide stearic acid, N- (3,5-carbamic acid
Di-tert-butyl-4-hydroxyphenyl) octyl ester.

1.13. β- (3,5-di-tertiary butyrate
One of the following 4- (4-hydroxyphenyl) propionic acid
Esters with polyhydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3, -Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14. β- (5-tert-butyl-4-
Hydroxy-3-methylphenyl) propionic acid below
Esters of monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane Diol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15. β- (3,5-di-cyclohexyl
Xyl-4-hydroxyphenyl) propionic acid below
Esters of monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol , Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate,
N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6.
7-trioxabicyclo [2.2.2] octane.

1.16. 3,5-di-tert-butyl-4
-The following monovalent or polyvalent alkanes of hydroxyphenylacetic acid
Esters with kohl, such as methanol, ethanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3, -Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. β- (3,5-di-tertiary butyrate
An amide of lu-4-hydroxyphenyl) propionic acid ,
For example, N, N'-bis (3,5-di-tert-butyl-4-
Hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-
Hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19 Amine Antioxidants For example, N, N′-diisopropyl-p-phenylenediamine, N, N′-tert-butyl-p-phenylenediamine, N, N′-bis- (1,4 -Dimethylpentyl)-
p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine,
N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (2 -Naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p
-Phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-
(1-Methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-
p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N,
N'-tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p '. -Di-tert-butyl-
Octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4
-Methoxyphenyl) amine, 2,6-di-tert-butyl-
Butyl-4-dimethylaminomethylphenol, 2,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane , 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1-naphthylamine, mono -And dialkylated tert-butyl / tert-octyldiphenylamine mixtures, mono- and dialkylated isopropyl / isohexyldiphenylamine mixtures, mono- and dialkylated tert-butyldiphenylamine mixtures, 2,3-dihydro-3,3- Dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothi Jin, N, N, N ', N'-
Tetraphenyl-1,4-diaminobute-2-ene,
N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl-hexamethylenediamine, bis (2,2,2
6,6-Tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4
-All.

2. UV absorbers and light stabilizers 2.1. 2- (2'-hydroxyphenyl) benzoto
Riazoles such as 2- (2'-hydroxy-5'-
Methylphenyl) benzotriazole, 2- (3 ',
5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-
Hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3',
5'-di-tert-butyl-2'-hydroxyphenyl)-
5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-
Chlorobenzotriazole, 2- (3'-tert-butyl-
5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'
-Di-tertiary amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'- Tertiary butyl-2'-hydroxy-5 '-(2'-octyloxycarbonylethyl)
Phenyl) -5-chlorobenzotriazole, 2-
(3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-
Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxy Carbonylethyl) phenyl)
Benzotriazole, 2- (3'-tert-butyl-2'-
Hydroxy-5 ′-(2-octoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-tert-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl) Benzotriazole, 2- (3-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5'-
A mixture of (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6.
-Benzotriazol-2-ylphenol], 2-
Transesterification product of [3′-tert-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] benzotriazole and polyethylene glycol 300, [R—CH ₂ CH ₂ —COO (CH ₂ ) ₃ −]
_2- (in the formula, R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl).

2.2. 2-hydroxy-benzopheno
Emissions, such as 4-hydroxy -, 4-methoxy -, 4-octoxy -, 4-decyloxy -, 4-dodecyloxy -, 4-benzyloxy -, 4,2 ', 4'-trihydroxy - or 2'Hydroxy-4,4'-dimethoxy derivative.

2.3. Substituted and unsubstituted benzoin
Esters of acids such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl =
Salicylate, dibenzoylresorcinol, bis (4
-Tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl =
3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl = 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl = 3,5-di-tert-butyl-4-hydroxybenzoate, 2 -Methyl-
4,6-di-tert-butylphenyl = 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylate , eg ethyl α
-Cyano-β, β-diphenyl-acrylate, isooctyl α-cyano-β, β-diphenyl-acrylate, methyl α-carbomethoxy-cinnamate, methyl α-cyano-β-methyl-p-methoxy-cinnamate, butyl α- Cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate, and N- (β-carbomethoxy-β-
Cyanovinyl) -2-methylindoline.

2.5. Nickel compounds , eg 2,
Nickel complexes of 2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], eg 1:
1 or 1: 2 complexes optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3 , 5-Di-tert-butylbenzylphosphonic acid monoalkyl ester such as the nickel salt of methyl or ethyl ester, ketoxime such as 2-hydroxy-4
-Methyl-phenyl undecyl ketoxime nickel complex, 1-phenyl-4-lauroyl-5-hydroxypyrazole nickel complex optionally with other ligands.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl)
Succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6)
-Pentamethylpiperidyl) n-butyl-3,5-di-
Tert-butyl-4-hydroxybenzyl malonate, 1-
Condensation product of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4 -Piperidyl) hexamethylenediamine and 4-tertiary octylamino-2,6-dichloro-1,3,5-s-
Condensation product with triazine, tris (2,2,6,6-
Tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-)
Piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-
Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2- n-Butyl-2- (2-hydroxy-3,5-di-tert-butyl-benzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [ 4.5] Decane-2,
4-dione, bis (1-octyloxy-2,2,6,
6-tetramethylpiperidyl) sebacate, bis (1-
Octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6)
-Tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3
Condensation product with 5-triazine, 2-chloro-4,6-
Bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2
-Bis (3-aminopropylamino) ethane condensation product, 2-chloro-4,6-di (4-n-butylamino-
1,2,2,6,6-pentamethylpiperidyl) -1,
Condensation product of 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione,
3-dodecyl-1- (2,2,6,6-tetramethyl-
4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4
-Piperidyl) -pyrrolidine-2,5-dione, 4-hexadecyloxy and 4-stearoyloxy-2,2
Mixture with 6,6-tetramethylpiperidine, N, N '
A condensation product of -bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylano-2,6-dichloro-1,3,5-triazine, 1,2- Condensation product of bis (3-aminopropylamino) ethane with 2,4,6-dichloro-1,3,5-triazine and 4-butylamino-2,2,6,6
-Tetramethylpiperidine (CAS Reg. No [1
36504-96-6]), N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4) −
Piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-
3,8-Diaza-4-oxo-spiro [4,5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4 , 5] Reaction product of decane and epichlorohydrin.

2.7. Oxamide , for example 4,4'-
Dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5 '
-Di-tertiary butoxanilide, 2,2'-didodecyloxy-5,5'-di-tertiary butoxanilide, 2-ethoxy-2'-ethoxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide , 2-Ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures of said compound with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p- Mixtures of methoxy-disubstituted oxanilide and o- and p-ethoxy-disubstituted oxanilide.

2.8. 2- (2-hydroxypheny
) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl)
-1,3,5-triazine, 2- (2-hydroxy-4)
-Octyloxyphenyl) -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine, 2-
(2,4-Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
Octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3)
-Butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2
-(2-hydroxy-4-dodecyloxy-phenyl)
-4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-
Hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,2
4-dimethyl) -1,3,5-triazine, 2- [4-
(Dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl-4,6-diphenyl-1) , 3,5-triazine,
2,4,6-Tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,
3,5-triazine, 2- (2-hydroxyphenyl)
-4- (4-methoxyphenyl) -6-phenyl-1,
3,5-triazine.

3. Metal deactivators , such as N, N'-
Diphenyl oxalic acid diamide, N-salicyral-N'-
Salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, N, N'-diacetal-adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid Dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide.

4. Phosphite and phosphonite ,
For example, triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritoldiphosphite, tris (2,
4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,2
4-di-tert-butylphenyl) -pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-
Methylphenyl) -pentaerythritol diphosphite, di-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite bis (2,4 , 6-Tris-tert-butyl-butylphenyl) -pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite, 6- Isooctyloxy-2,
4,8,10-Tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl- 12
-Methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-
Tert-butyl-6-methylphenyl) ethylphosphite.

5. Hydroxylamine such as N, N-
Dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-
From ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, hydrogenated tallow amine Derived N, N-dialkylhydroxylamine.

6. Nitrones, for example N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone,
N-tetradecyl-alpha-tridecyl nitrone, N
-Hexadecyl-alpha-pentadecyl nitrone, N
-Octadecyl-alpha-heptadecyl nitrone, N
-Hexadecyl-alpha-heptadecyl nitrone, N
-Octadecyl-alpha-pentadecyl nitrone, N
-Heptadecyl-alpha-heptadecyl-nitrone,
N-octadecyl-alpha-hexadecyl-nitrone, a nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers , eg β
Esters of thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles, or zinc salts of 2-mercaptobenzimidazoles, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritoltetrakis (β-dodecylmercapto) ) Propionate.

9. Polyamide stabilizers , for example copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

10. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and alkaline earth metal salts such as Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate and K palmitate, catechol antimony salt and catechol tin salt.

11. Nucleating agents such as inorganic substances, for example metal oxides such as talc, titanium dioxide or magnesium oxide, preferably alkaline earth metal phosphates, carbonates or sulphates; organic compounds such as mono- or polycarboxylic acids and Polymerizable compounds such as salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; ionic copolymers (“ionomers”).

12. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheology add
positives), catalysts, flow control agents, brighteners, flame retardants, antistatic agents and blowing agents.

14. Benzofuranone or indolino
Down, for example, U.S. Pat invention herein (US-A-) No. 432
No. 5863, No. 4338244, No. 517531.
No. 2, No. 5216052, No. 5252643,
German patent application publication specification (DE-A-) 43166
No. 11, No. 4316622, No. 4316876
Issue, European Patent Office publication (EP-A-) No. 058
Those described in No. 9839 or No. 0591102 or 3- [4- (2-acetoxyethoxy)
Phenyl] -5,7-di-tert-butyl-benzofurano-
2-one, 5,7-di-tert-butyl-3- [4- (2-
Stearoyloxyethoxy) phenyl] benzofurano-2-one, 3,3′-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofurano-2-one], 5 , 7-di-tert-butyl-3
-(4-ethoxyphenyl) benzofurano-2-one,
3- (4-acetoxy-3,5-dimethylphenyl)-
5,7-di-tert-butyl-benzofurano-2-one, 3
-(3,5-Dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofurano-2-one.

The compounds of formula (I) are also known as stabilizers, in particular those known to the person skilled in the art of photocopying and other reproduction arts, for example Research Disclosure (Reserch).
It can also be used as a light stabilizer for almost all materials described in Disclosure 1990, 31429 (pages 474 to 480).

Some preparations and uses of the compounds of formula (I) are described for a more detailed explanation of the invention. These examples are provided for purposes of illustration and are not limiting in any way.

The compounds of formula (I) are particularly useful for stabilizing polypropylene fibers. Examples 1, 3 below
The compounds of 4 and 5 are of particular interest.

Example 1: The following equation

[Chemical 10] The production of a compound represented by: 1,2-dichloroethane 55
N- (2,2,6,6-tetramethyl-4-in 0 ml
Piperidyl) -2,2,6,6-tetramethyl-4-piperidylamine A solution containing 286.4 g (1 mol) of a cyanuric chloride 184.5 g (1 mol) in 1000 ml of 1,2-dichloroethane is added to a mixture. Add slowly at 0 ° C. When the addition is complete, add 2
It was stirred for a period of time at room temperature, then cooled to 10 ° C. and a solution of 40 g (1 mol) of sodium hydroxide in 120 ml of water was added thereto.

The mixture was stirred for 2 hours at room temperature, filtered and the solid residue washed twice with 300 ml of water. 1,
1500 ml of 2-dichloroethane, 34.4 g (0.33 mol) of diethylenetriamine and 4 g (1 mol) of sodium hydroxide dissolved in 120 ml of water were then added at room temperature.

The mixture thus obtained is stirred for 8 hours for 2 hours.
Heat to 0 ° C., separate the aqueous phase and wash the organic layer with water.

After evaporation of the solvent, N-butyl-2,
2,6,6-Tetramethyl-4-piperidylamine 21
2.4 g (1 mol), 80 g (2 mol) of sodium hydroxide and 2000 ml of trimethylbenzene were added.
The mixture was then heated at reflux for 12 hours and the water of reaction was removed by azeotropic distillation. The mixture was filtered, the organic solution was washed with water, the solvent was evaporated and the residue was crystallized from acetonitrile. A product with a melting point of 166 ° -173 ° C. was obtained. Elemental analysis of C ₁₀₆ H ₁₉₉ N ₂₇ Calculated: C = 68.75%, H = 10.83%, N = 2
0.42% Experimental value: C = 68.47%, H = 10.81%, N = 2
0.06%

Example 2: By the procedure described in Example 1 (1,5,8,12-instead of diethylenetriamine)
(Excluding the use of tetraazadodecane), melting point 17
The following formula of 8 to 183 ℃

[Chemical 11] A compound represented by Elemental analysis of C ₁₄₄ H ₂₇₀ N ₃₆ Calculated: C = 69.02%, H = 10.86%, N = 2
0.12% Experimental value: C = 67.87%, H = 10.66%, N = 1
9.82%

Example 3: The following equation

[Chemical 12] The production of a compound represented by: N-butyl-2,2,6,6
-Tetramethyl-4-piperidylamine 100 g (0.
47 mol) over 1 hour with trimethylbenzene 600
Added to 87 g (0.47 mol) of cyanuric chloride in ml. At the end of the addition, the mixture was stirred for 1 hour at room temperature. After cooling to 5 ° C, sodium hydroxide 2
100 ml of an aqueous solution containing 0 g (0.5 mol) were added. The mixture so obtained was kept for 1 hour at room temperature, the phases were separated and the organic layer was washed with water. 1,12-bis (2,2,6,6-tetramethyl-4-piperidyl) -dissolved in 200 ml of trimethylbenzene
53.1 g of 1,5,8,12-tetraazadodecane
(0.12 mol), and 68 g of potassium carbonate (0.5
Mol) was then added and the mixture heated at 80 ° C. for 6 hours. 40 g (1 mol) of sodium hydroxide and N-
After adding 100 g (0.47 mol) of butyl-2,2,6,6-tetramethyl-4-piperidylamine, the mixture was heated at reflux for 16 hours. Upon completion of the reaction, the mixture was washed several times with water and the solvent was evaporated, mp 167
The product was obtained at ˜171 ° C. Elemental analysis of C ₁₄₂ H ₂₆₈ N ₃₄ Calculated value: C = 69.56%, H = 11.02%, N = 1
9.42% Experimental value: C = 69.26%, H = 10.83%, N = 1
9.30%

Example 4: The following equation

[Chemical 13] The production of a compound represented by: 4.3 g of formaldehyde (containing no methanol) in 50 ml of water (0.
144 mol) and 6.6 g (0.144 mol) of formic acid are added over 2 hours to a solution of 29.4 g (0.012 mol) of the product from Example 3 in 150 ml of xylene and reflux. The mixture was heated and, at the same time, water and reaction water added by azeotropic distillation were removed. After cooling to room temperature, a solution of 5.8 g of sodium hydroxide in 50 ml of water is added,
The mixture was stirred for 15 minutes and the aqueous phase was separated. The organic phase was washed with water and the solvent was evaporated to give the product, mp 177-180 ° C. Elemental analysis of C ₁₇₂ H ₂₈₈ N ₃₄ Calculated: C = 70.43%, H = 11.20%, N = 1
8.37% Experimental value: C = 69.58%, H = 10.98%, N = 1
8.28%

Example 5: The procedure as described in Example 4 was carried out (but using the product from Example 1 in place of the product from Example 3 and adjusting to the appropriate molar ratio). The melting point of 203 to 208 ° C.

Embedded image A compound represented by Elemental analysis of C ₁₁₅ H ₂₁₇ N ₂₇ Calculated: C = 69.83%, H = 11.06%, N = 1
9.12% Experimental value: C = 69.76%, H = 10.94%, N = 1
9.02%

Example 6: The procedure is as described in Example 4 (but the product from Example 2 is used in place of the product from Example 3 and adjusted to the appropriate molar ratio). The melting point of 212 to 218 ° C.

[Chemical 15] A compound represented by Elemental analysis of C ₁₅₆ H ₂₉₄ N ₃₆ Calculated value: C = 70.06%, H = 11.08%, N = 1
8.85% Experimental value: C = 69.50%, H = 10.92%, N = 1
8.85%

Example 7: Light-stabilizing action on polypropylene fibers 2.5 g of the product of Example 3, 1 g of tris (2,4-di-tert-butylphenyl) phosphite, monoethylcalcium 3,5-di- 0.5 g of tert-butyl-4-hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide, melt index = 1
Mixed in a low speed mixer with 1000 g of polypropylene in powder form having 2 g / 10 min (measured at 230 ° C. and 2.16 kg). The mixture is extruded at 200 to 230 ° C. to obtain polymer granules, which are subsequently fed to semi-industrial equipment [Leonard-Smirago.
-Sumirago) (VA), Italy] and processed under the following conditions: Extrusion temperature: 200 to 230 ° C. Head temperature: 255 to 260 ° C. Stretching ratio: 1: 3.5 Filament density: 11 dtex (filament under density) The fibers thus produced were installed on white cardboard and then at 63 ° C. Exposed in a model 65WR weatherometer (ASTM D2565-85) at black panel temperature. The residual tenacity of the samples taken after various light exposure times was measured using a constant speed tensile tester and the obtained values were used to determine the initial toughness.
The exposure time (T ₅₀ ) required to reduce the tial tenacity) by half (50%) was calculated. For comparison, fibers made under conditions similar to those shown above without the inventive stabilizer were exposed. The results obtained are shown in Table 1. Table 1 Stabilizer T ₅₀ (hours ) No stabilizer 240 Compound of Example 3 1900

Example 8: Light-stabilizing action on polypropylene fibers after heat treatment The fibers prepared in Example 7 are exposed in an oven for 20 minutes at 120 ° C. and then after installation on white cardboard, a black panel at 63 ° C. Exposure at temperature in a model 65WR weatherometer (ASTM D2565-85). The residual tenacity of the samples taken after various light exposure times was measured using a constant speed tensile tester and the obtained values were used to determine the initial toughness.
The exposure time (T ₅₀ ) required to reduce the tial tenacity) by half (50%) was calculated. For comparison, fibers made under conditions similar to those shown above without the inventive stabilizer were exposed. The obtained results are shown in Table 2. Table 2 Stabilizer T ₅₀ (hours ) No stabilizer 150 Compound of Example 3 1802

Example 9: Light-stabilizing action on polypropylene fibers 2.5 g of the product of Table 3, 1 g of tris (2,4-di-tert-butylphenyl) phosphite, monoethylcalcium 3,5-di-third 0.5 g of tributyl-4-hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide, melt index = 12 g
Mixed in a low speed mixer with 1000 g of polypropylene in powder form having / 10 min (measured at 230 ° C. and 2.16 kg). The mixture is extruded at 200 to 230 ° C. to obtain polymer granules, which are subsequently subjected to semi-industrial equipment (trade name Leonard-Sumirago.
(Irago) (VA), Italy] and processed under the following conditions. Extrusion temperature: 200 to 230 ° C. Head temperature: 255 to 260 ° C. Stretching ratio: 1: 3.5 Filament density: 11 dtex (filament linear density) After installing the fiber thus produced on white cardboard, 6
Exposed in a model 35WR weatherometer (ASTM D2565-85) at a black panel temperature of 3 ° C.
Residual toughness for samples taken after various light exposure times
(recidual tenacity) was measured using a constant-speed tensile tester, and the initial toughness (initial t
Exposure time required to halve (50%) enacity (T
₅₀ ) was calculated. For comparison, fibers made under conditions similar to those shown above without the inventive stabilizer were exposed. Table 3 shows the obtained results. Table 3 Stabilizer T ₅₀ (hours ) No stabilizer 250 Compound of Example 4 2100 Compound of Example 5 2510 Compound of Example 6 2240

Example 10: Light-stabilizing action on polypropylene fibers after heat treatment The fibers prepared in Example 9 were exposed to 120 ° C. for 20 minutes in an oven and then mounted on white cardboard, then 63
Exposed in a Model 35WR weatherometer (ASTM D2565-85) at a black panel temperature of ° C. Residual toughness (r
ecidual tenacity) was measured using a constant-speed tensile tester and the obtained values were used to determine the initial tenacity.
The exposure time (T ₅₀ ) required to halve (50%) the acity) was calculated. For comparison, fibers made under conditions similar to those shown above without the inventive stabilizer were exposed. The results obtained are shown in Table 4. Table 4 Stabilizer T ₅₀ (hours ) No stabilizer 150 Compound of Example 4 2130 Compound of Example 5 2220 Compound of Example 6 2060

Example 11: Light stabilizing effect on polypropylene tape 1 g of the compound in Table 5, 1.0 g of tris (2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] 0.5 g and calcium stearate 1 g, melt index = 1.
Mixed in a low speed mixer with 1000 g of polypropylene in powder form having 2 g / 10 min (measured at 230 ° C. and 2.16 kg). The mixture is extruded at 200 to 220 ° C. to obtain polymer granules, which are subsequently fed into semi-industrial equipment [Leonard-Schmirago.
-Sumirago) (VA), Italy], and operated under the following conditions to form a stretch tape having a thickness of 50 μm and a width of 2.5 mm. Extrusion temperature: 210 to 230 ° C. Head temperature: 240 to 260 ° C. Stretching ratio: 1: 6 The fibers thus produced were installed on white cardboard and then at a black panel temperature of 63 ° C., a model 65WR weatherometer ( Exposed in ASTM D2565-85). The residual tenacity of the samples taken after various light exposure times was measured using a constant speed tensile tester and the obtained values were used to determine the initial toughness.
The exposure time (T ₅₀ ) required to reduce the tial tenacity) by half (50%) was calculated. For comparison, fibers made under conditions similar to those shown above without the inventive stabilizer were exposed. Table 5 shows the obtained results. Table 5 Stabilizer T ₅₀ (hours ) No stabilizer 320 Compound of Example 3 1800

Example 12: Light-stabilizing action on polypropylene tape Model 35WR weatherometer (ASTM D2565)
The procedure described in Example 11, except using -85), gave the results shown in Table 6. Table 6 Stabilizer T ₅₀ (hours ) No stabilizer 340 Compound of Example 1 2100 Compound of Example 5 2000

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07D 251: 54) (72) Inventor Roberto Sucrima 40126 Bologna Via del Borgoges, Italy. Pietro 132

Claims (17)

[Claims] 1. The following formula (I): [In the formula, n represents 0 or 1, and X represents the following formula (I
I) [Chemical formula 2] R ₁ and R ₅ may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, unsubstituted or 1, 2 or 3 carbon atoms having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms substituted by an alkyl group of 7 to 7 carbon atoms which is unsubstituted or substituted on the phenyl group by an alkyl group having 1, 2 or 3 carbon atoms of 1 to 4 9 represents a phenylalkyl group, or R ₁ and R ₅ are represented by the following formula (III): And R ₂ , R ₃ and R ₄ may be the same or different and each represents an alkylene group having 2 to 12 carbon atoms, R ₆ is a hydrogen atom or alkyl having 1 to 18 carbon atoms. Groups, unsubstituted or substituted with 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, alkenyl groups having 3 to 6 carbon atoms, unsubstituted or phenyl Represents a phenylalkyl group having 7 to 9 carbon atoms, which is substituted by an alkyl group having 1 to 2 or 3 carbon atoms and having 1 to 4 carbon atoms, and R ₇ is a hydrogen atom or 1 carbon atom
To 8 _{alkyl, O ·, OH, CH 2} CN, alkoxy groups of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, an alkenyl group of 6 C 3 -C, unsubstituted or phenyl Represents a phenylalkyl group having 7 to 9 carbon atoms which is substituted by 1, 2 or 3 alkyl group having 1 to 4 carbon atoms, or R ₇ is an aliphatic group having 1 to 8 carbon atoms. When an acyl group is represented, n is 1 and R ₁ and R ₅ are groups of the formula (III), X is of the formula (IV) (In the formula, R ₆ and R ₇ have the same meanings as previously defined). ] The compound represented by these. 2. R ₇ is a hydrogen atom or 1 to 4 carbon atoms.
An alkyl group, OH, an alkoxy group having 6 to 12 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms,
A compound of formula (I) according to claim 1 which represents an allyl group, a benzyl group or an acetyl group. 3. A compound of formula (I) according to claim 1, wherein R ₇ represents a hydrogen atom or a methyl group. 4. A compound of formula (I) according to claim 1, wherein X is a group of formula (II). 5. In the formula, X represents a group of formula (II), R ₁
And R ₅ may be the same or different and represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkylene group having 2 to 6 carbon atoms, and R ₆ is a hydrogen atom,
2. An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms. A compound of formula (I). 6. In the formula, X represents a group of formula (II), R ₁
And R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group or a benzyl group, and R ₂ , R ₃ and R ₄
Are the same or different and represent an alkylene group having 2 to 6 carbon atoms, and R ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, an allyl group or a benzyl group. A compound of formula (I) according to item 1. 7. In the formula, X represents a group of formula (II), R ₁
And R ₅ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
₂ , R ₃ and R ₄ may be the same or different,
2. A compound of formula (I) according to claim 1, wherein R ₆ represents an alkylene group having 2 to 3 carbon atoms, R ₆ represents an alkyl group having 1 to 4 carbon atoms, and R ₇ represents a hydrogen atom or a methyl group. Compound. Wherein said ^{compound, N I, N II, N} III - tris [2- (N- (2,2,6,6- tetramethyl-piperidine-dinitrate-4-yl) - butylamino) -4- (bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] amino) - triazinyl-6-yl] - ^{diethylenetriamine, N I, N II, N} III - tris [2-(N-
(1,2,2,6,6-pentamethylpiperidin-4-
Yl) -Butylamino) -4- (bis [1,2,2,
6,6-Pentamethylpiperidin-4-yl] amino)
-Triazin-6-yl] -diethylenetriamine, N
^I , N ^II , N ^III , N ^IV -Tetrakis [2- (N-
(2,2,6,6-Tetramethylpiperidin-4-yl) -butylamino) -4-bis [2,2,6,6-tetramethyl-piperidin-4-yl] amino-triazin-6- yl] -1,5,8,12- tetraazacyclododecane dodecane, or ^{N I, N II, N III} , N IV - tetrakis [2- (N- (1,2,2,6,6- pentamethyl piperidine Gini -4-yl) -Butylamino) -4- (bis [1,2,2,6,6-pentamethyl-piperidin-4]
-Yl] amino) -triazin-6-yl] -1,5
A compound of formula (I) according to claim 1 which is 8,12-tetraazadodecane. 9. The formula (I) according to claim 1, wherein n represents 1, R ₁ and R ₅ represent a group of formula (III) and X represents a group of formula (IV). ) Compound. 10. In the formula, n represents ₁ and R ₁ and R ₅
Represents a group of formula (III), X represents a group of formula (IV), R ₂ , R ₃ and R ₄ may be the same or different and represent an alkylene group having 2 to 6 carbon atoms, and R ₆ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms or 7 carbon atoms.
Claim 1 which represents a phenylalkyl group of 1 to 9
A compound of formula (I) as described. 11. In the formula, n represents ₁ and R ₁ and R ₅
Represents a group of formula (III), X represents a group of formula (IV), R ₂ , R ₃ and R ₄ may be the same or different and represent an alkylene group having 2 to 6 carbon atoms, and The compound of formula (I) according to claim 1, wherein R ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, an allyl group or a benzyl group. 12. In the formula, n represents ₁ and R ₁ and R ₅
Represents a group of formula (III), X represents a group of formula (IV), R ₂ , R ₃ and R ₄ may be the same or different and represent an alkylene group having 2 to 3 carbon atoms, R
₆ represents an alkyl group of 1 to 4 carbon atoms, and R ₇ is a compound of formula (I) according to claim 1 where represents a hydrogen atom or a methyl group. Wherein said compound, N ^I, N ^IV - bis [2,2,6,6-tetramethyl-piperidine-dinitrate-4-yl] ^{-N I, N II, N III} , N IV - tetrakis - [ Two
4-bis [N- (2,2,6,6-tetramethyl-piperidin-4-yl) -butylamino] -triazin-6
- yl] -1,5,8,12- tetraazacyclododecane dodecane, or N ^I, N ^IV - bis [1,2,2,6,6 pentamethyl piperidine Gini-4-yl] -N ^I, N ^II , N ^III ,
N ^IV -tetrakis- [2,4-bis [N- (1,2,
2,6,6-Pentamethyl-piperidin-4-yl)-
Butylamino] -triazin-6-yl] -1,5
A compound of formula (I) according to claim 1 which is 8,12-tetraazadodecane. 14. An organic material susceptible to decay induced by light, heat or oxidation, and at least 1.
A composition comprising a compound of formula (I) as described. 15. The composition of claim 14, wherein the organic material is a synthetic polymer. 16. A composition according to claim 15, which comprises, in addition to the compound of formula (I), other additives customarily present in synthetic polymers. 17. The composition according to claim 14, wherein the organic polymer is polyethylene or polypropylene.